Supported polymerization catalyst using a catalyst precursor having functional group and surface modified carrier and olefin polymerization using the same

ABSTRACT

Support within the disclosure of the present application can only be found for the treatment of the dehydrated silica catalyst carrier with a silazane compound and not with a silane compound. The search has therefore been restricted to silazane treated silica supports

BACKGROUND OF THE INVENTION

[0001] (a) Field of the Invention

[0002] The present invention relates to a supported metallocene catalystusing a metallocene compound having a functional group easy to prepare asupported metallocene catalyst for an olefin polymerization, and anolefin polymerization process using the supported catalyst.

[0003] (b) Description of the Related Art

[0004] In 1976, a German professor Kaminsky has reported thatmethylaluminoxane (MAO) compound obtained from partial hydrolysis oftrimethylaluminum can be used as a cocatalyst and zirconocenedichloridecompound can be used as a catalyst in an olefin polymerization (A.Anderson, J. G. Corde, J. Herwig, W. Kaminsky, A. Merck, R. Mottweiler,J. Pein, H. Sinn, and H. J. Collmer, Angew Chem, Int. Ed. Edgl., 15,630, 1976).

[0005] Afterwards, Exxon has revealed that molecular weight and activityof a produced polymer can be controlled by changing substituents oncyclopentadienyl ligand, and applied for a patent (U.S. Pat. No.5,324,800) regarding an olefin polymerization using a metallocenecompound having various substituents.

[0006] The homogeneous olefin polymerization catalyst shows uniquepolymerization properties that cannot be embodied by the existingZiegler-Natta catalyst. Namely, a molecular weight distribution ofproduced polymer is narrow, copolymerization is easy, and a distributionof the second monomer is uniform. For propylene polymerization,stereoselectivity of a polymer can be controlled according to thesymmetry of a catalyst. These unique properties made it possible tosynthesize a novel polymer that could not be obtained by the existingZiegler-Natta catalyst and also made it possible to prepare a resin withphysical properties required by consumers. For these reasons, saidcatalyst is actively studied.

[0007] In a gas-phase process or a slurry process, a particle shape orapparent density of a polymer should be controlled in order to increasefluidity of polymer and yield of reactor per unit volume, and foulingproblem, adhesion of polymer to a wall surface of a reactor, should beremoved for continuous operation. In order to solve these problems, ametallocene catalyst should be supported in an appropriate carrier.

[0008] Generally, known processes for preparing a supported metallocenecatalyst are as follows:

[0009] A metallocene compound is physically adsorbed and supported on acarrier, and then contacted with aluminoxane (W. Kaminsky, Makromol.Chen., Rapid Commun. 14, 239 (1993));

[0010] Aluminoxane is supported on a carrier and then a metallocenecompound is supported thereon (Soga K., Makromol. Chen. Rapid Commn.,13, 221 (1992); U.S. Pat. No. 5,006,600; U.S. Pat. No. 5,086,025);

[0011] A metallocene compound is contacted with aluminoxane and then itis supported on a carrier (U.S. Pat. No. 5,240,892).

[0012] It is also known that a part of a ligand of a metallocenecompound is chemically bonded to a carrier to prepare a supportedmetallocene catalyst. It is known that, in order to prepare a supportedmetallocene catalyst, a ligand is attached to a carrier surface througha chemical bond and then a metal is attached to the ligand (K. Soga, H.J. Kim, T. Shiono, Makromol, Rapid Commun. 15, 139 (!994), JapanesePatent Publication Hei 6-56928, U.S. Pat. No. 5,466,766).

[0013] It is also known that a metallocene compound having functionalgroups easy to react with a carrier is firstly prepared and then it isreacted with a carrier to prepare a supported metallocene catalyst.Wherein silicone-based functional groups such as alkoxysilane andhalosilane are mainly used (E.P. Laid-open Publication No. 293815, U.S.Pat. No. 5,767,300, E.P. Laid-open Publication No. 839836, Korean PatentApplication Nos. 98-12660 and 99-06955). However, these metallocenecompounds having silicone-based functional groups are not easy tosynthesize and the stability thereof are not good. For examples, E.P.Laid-open Publication No. 839836 describes a metallocene compound havingOSiMe₃ functional group, but it cannot be commercially used because anyield of the last step for introducing zirconium is unfavorable as28˜51%.

[0014] U.S. Pat. No. 5,814,574 has disclosed a polymerization catalystsupported by binding a metallocene compound having Lewis acid functionalgroups selected from alkoxy alkyl, heterocycle oxygen radical or alkylheterocycle oxygen radical to an inorganic carrier. U.S. Pat. No.5,767,209 has described a preparation of a supported catalyst by bindinga metallocene compound having functional groups with Lewis basicityincluding oxygen, silicone, phosphorous, nitrogen or sulfur to aninorganic carrier in the absence of aluminoxane, and a polymerizationprocess by contacting the catalyst with at least one olefin at pressureand temperature sufficient to cause a polymerization. However, forbinding to an inorganic carrier through a functional group with Lewisbasicity, a carrier surface must have Lewis acidity. Referring to theExamples of the Patents, in order to give Lewis acidity to the surfaceof a carrier such as silica, butylmagnesium chloride and TiCl₄ aretreated or diethylaluminum chloride is treated. In addition, thecatalyst bound to the surface through a functional group having Lewisbasicity, if activated with a cocatalyst having Lewis acidity such asaluminoxane, is separated from the surface and causes reactor fouling,and a particle shape of a polymer produced therefrom is not good, andthus it is difficult to use in a slurry process or a gas-phase process.

SUMMARY OF THE INVENTION

[0015] The present invention is made in consideration of the problems ofthe prior art and it is an object of the present invention to provide asupported metallocene catalyst wherein a metallocene catalyst easy tochemically bond to a carrier is supported on a carrier which surface ismodified with chemicals, and an olefin polymerization process using thesame.

[0016] It is another object of the present invention to provide asupported metallocene catalyst that does not cause reactor foulingbecause it is not separated when polymerizing an olefin and has superiorpolymerization activity, and an olefin polymerization process using thesame.

[0017] It is another object of the present invention to provide asupported metallocene catalyst that can prepare an olefin polymer whichparticle shape follows an unique shape of a carrier and has superiorapparent density, and an olefin polymerization using the same.

[0018] In order to achieve these objects, the present invention providesa supported metallocene catalyst wherein a metallocene compound issupported on a carrier by contact reacting

[0019] a) one or more kinds of metallocene compound catalyst ingredientwherein at least one hydrogen radical existing on R¹, R² or B of ametallocene compound represented by the following Chemical Formula 1 or2 is substituted with an organic radical selected from radicalsrepresented by the following Chemical Formula 3, 4 and 5; and

[0020] b) a carrier, in the presence of an organic solvent

[0021] to break a carbon-oxygen bond, a carbon-sulfur bond or asilicone-oxygen bond existing on a radical represented by the ChemicalFormula 3, 4 or 5 of the a) metallocene compound catalyst ingredient

[0022] thereby forming a novel chemical bond between the a) metallocenecompound and the b) carrier,

[0023] characterized in that the b) carrier is a silica prepared bysilane-treating a silica dehydrated at a temperature of 500° C. or moreto selectively remove hydroxy groups out of hydroxy groups and siloxanegroups existing on a silica surface:

(C₅R¹ _(m))_(p)B_(s)(C₅R¹ _(m))MQ_(3-p)  [Chemical Formula 1]

[0024] [Chemical Formula 2]

[0025] (In the Chemical Formula 1 or 2,

[0026] M is a Group 4 transition metal;

[0027] Each of (C₅R¹ _(m)) and (C⁵R¹ _(n)) is a cyclopentadineyl orsubstituted cyclopentadienyl, wherein each R¹, which may be identical ordifferent, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl, arylalkenyl radical or hydrocarbyl-substituted 14Group metalloid; or a substituted cyclopentadineyl ligand wherein twoneighboring carbon atoms in C₅ are connected each other through ahydrocarbyl radical to form one or more 4-16 angular rings;

[0028] B, which is a bridge connecting two cyclopentadienyl ligands, orone cyclopentadienyl ligand and JP² _(z-y) though covalent bonds, iscarbon chain alkylene, carbon chain arylene, carbon cahin alkenylene,dialkylsilicone, dialkylgermanium, alkyl phophine or alkylamine,

[0029] R² is a hydrogen radical, C1-40 alkyl radical, alkenyl radical,aryl radical, alkylaryl radical, or arylalkyl radical;

[0030] J is VA Group atom or VIA Group atom;

[0031] Q, which may be identical or different, is halogen radical, C1-20alkyl radical, alkenyl radical, aryl radical, alkylaryl radical,arylalkyl radical or C1-20 alkylidene radical;

[0032] L is a Lewis base;

[0033] s is 0 or 1, p is 0, 1 or 2, provided that s is 0 when p is o, mis 4 when s is 1, and m is 5 when s is 0;

[0034] z, which is an atomic valence of J, is 3 for VA Group atoms, and2 for VIA Group atoms; and

[0035] x is 0 or 1, provided that when x is 0, n is 5, y is 1 and w ismore than 0, and when x is 1, n is 4, y is 2 and w is 0.)

[0036] [Chemical Formula 3]

[0037] Z is an oxygen or sulfur atom;

[0038] R, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl orarylalkenyl radical;

[0039] R′, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl,arylalkenyl radical, and two R′ may be connected each other to form aring;

[0040] Y is C1-40 alkoxy, aryloxy, alkylthio, arylthio, phenyl orsubstituted phenyl, and it may be connected with R′ to form a ring; and

[0041] A is a carbon or silicone atom,

[0042] provided that Y must be alkoxy or aryloxy, when Z is a sulfuratom, and Z must be an oxygen atom when Y is alkylthio, arylthio, phenylor substituted phenyl.)

[0043] [Chemical Formula 4]

[0044] Z is an oxygen or sulfur atom, and at least one of Z is an oxygenatom;

[0045] R″ is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl or arylalkenyl radical, and it may be connectedwith R′″ to form a ring;

[0046] R′″, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl orarylalkenyl radical, and two R′″ may be connected each other to form aring; and

[0047] A is carbon or silicone atom.)

[0048] [Chemical Formula 5]

[0049] R″″, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl orarylalkenyl radical;

[0050] R′″″, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl orarylalkenyl radical, and two neighboring R′″″ may be connected eachother to form a ring;

[0051] provided that all R′″″ is not an hydrogen radical when at leastone R″″ is an hydrogen radical, and all R″″ is not an hydrogen radicalwhen at least one R′″″ is an hydrogen radical.; and

[0052] A is a carbon or silicon atom.)

[0053] The present invention also provides an olefin polymerizationprocess using a catalyst system comprising

[0054] a) a supported metallocene catalyst wherein a metallocenecompound is supported on a carrier by contact reacting

[0055] i) one or more kinds of metallocene compound catalyst ingredientwherein at least one hydrogen radical existing on R¹, R² or B of ametallocene compound represented by the following Chemical Formula 1 or2 is substituted with an organic radical selected from a groupconsisting of radical represented by the following Chemical Formula 3,radical represented by the following Chemical Formula 4 and radicalrepresented by the following Chemical Formula 5; and

[0056] ii) a carrier, in the presence of an organic solvent

[0057] to break a carbon-oxygen bond, a carbon-sulfur bond or asilicone-oxygen bond existing on the radical represented by the ChemicalFormula 3, 4 or 5 of the i) metallocene compound catalyst ingredient

[0058] thereby forming a novel chemical bond between i) the metallocenecompound and ii) the carrier; and

[0059] b) one or more kinds of cocatalyst selected from a groupconsisting of a compound represented by the Chemical Formula 6, acompound represented by the Chemical Formula 7 and a compoundrepresented by the Chemical Formula 8,

[0060] characterized in that the a) ii) carrier is a silica prepared bysilane-treating a silica dehydrated at a temperature of 500° C. or moreto selectively remove hydroxy groups out of hydroxy groups and siloxanegroups existing on a silica surface:

[0061] [Chemical Formula 6]

[0062] R³, which may be identical or different, is an halogen radical,C1-40 hydrocarbyl radical or halogen-substituted C1-40 hydrocarbylradical, and

[0063] d is an integer of 2 or more.)

Al(R⁴)₃  [Chemical Formula 7]

[0064] (In the Chemical Formula 7,

[0065] R⁴, which may be identical or different, is halogen radical,C1-40 hydrocarbyl radical or halogen-substituted C1-40 hydrocarbylradical.)

[L]⁺[NE₄]⁻  [Chemical Formula 8]

[0066] (In the Chemical Formula 8,

[0067] [L]⁺ is a cation consisting of inorganic organic group;

[0068] N is a Group 13 atom in Periodic Table; and

[0069] E, which may be identical or different, is C6-40 aryl radical,substituted with one or more of halogen radical, C1-40 hydrocarbylradical, alkoxy, phenoxy radical, C1-40 hydrocarbyl radical comprisingnitrogen, phosphorus, sulfur and oxygen atoms.)

[0070] In the polymerization process, the b) cocatalyst is preferablyone or more kinds of compounds selected from a compound represented byChemical Formula 6 and a compound represented by the Chemical Formula 7.

[0071] In addition, the a) i) metallocene catalyst ingredient ispreferably [Z-O—(CH₂)_(a)—C₅H₄]₂ZrCl₂ (wherein, a is 4˜8, and Z isselected from a group consisting of methoxymethyl, t-butoxymethyl,tetrahydropyranyl, tetrahydofuranyl, 1-ethoxyethyl,1-methyl-1-mehtoxyethyl and t-butyl), and the b) cocatalyst ispreferably one or more kinds of compounds selected from a compoundrepresented by the Chemical Formula 6 and a compound represented by theChemical Formula 7.

[0072] In addition, the polymerization process is preferably slurrypolymerization or gas-phase polymerization.

[0073] The silane is preferably an organosilane represented by theChemical Formula 9 or Chemical Formula 10:

(R₃Si)₂NH  [Chemical Formula 9]

R_(n)SiX_(4-n)  [Chemical Formula 10]

[0074] (In the Chemical Formula 9 or 10,

[0075] n is 1, 2 or 3;

[0076] X is an halogen; and

[0077] R is hydrogen radical or hydrocarbyl functional group.)

DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS

[0078] The present invention will now be explained in detail.

[0079] The present invention provides a supported metallocene catalystwherein a metallocene compound represented by the above Chemical Formula1 or 2 easy to prepare a supported catalyst, wherein at least onehydrogen radical existing on R¹, R² or B of Chemical Formula 1 andChemical Formula 2 is substituted with a radical selected from a groupconsisting of a radial represented by the Chemical Formula 3, a radicalrepresented by the Chemical Formula 4 and a radical represented by theChemical Formula 5, is supported on a silica carrier prepared bytreating a silica dehydrated at a temperature of 500° C. or more withsilane to selectively remove hydroxy groups out of hydroxy groups andsiloxane groups existing on a silica surface, and an olefinpolymerization process using the supported metallocene catalyst.

[0080] Namely, a metallocene compound, which substantially has acetal,ketal, secondary or tertiary alkoxyalkyl, benzyloxy alkyl, substitutedbenzyloxy alkyl, aryloxy alkyl, dithioacetal, dithioketal,monothioacetal, monothioketal, thioether, or alkoxy silane functionalgroup on a part of its ligand by substituting at least one hydrogenradical existing on R¹, R² or B of the Chemical Formula 1 or 2 with aradical of the Chemical Formula 3, 4 or 5, is chemically reacted withsiloxane group on the surface of a silica without hydroxy groups toprepare a supported catalyst, and the supported catalyst is used for anolefin polymerization.

[0081] The supported metallocene catalyst of the present invention isprepared by reacting the metallocene compound with a silica that issilane-treated after dehydrated at 500° C. or more.

[0082] Generally, a silica dehydrated at 500° C. or more has veryreactive siloxane group which is known to react with a compound havingan alkoxysilane functional group as shown in the following Equation 1(J. Am. Chem. Soic. 1995, vol 117, 2112, J. Am. Chem. Soc. 1993, vol115, 1190). And a patent for a supported metallocene catalyst using thereactivity of the silica dehydrated at high temperature withalkoxysilane group has been already applied (Korean Patent ApplicationNos. 98-12660, 99-06955, E.P. Laid-open Publication No. 839836)

[0083] It is also known in Korean Laid-open Patent Publication No.2001-3325 that a very reactive siloxane group dehydrated at hightemperature can react with acetal, ketal, tertiary alkoxy alkyl,benzyloxy alkyl, substituted benzyloxy alkyl, monothioacetal ormonothioketal functional group to break carbon-oxygen bond orcarbon-sulfur bond existing on the functional group to form a novelchemical bond with a surface.

[0084] Following Equation 2, 3, or 4 shows an example of a reactionpossibly caused by the metallocene compound of the present inventionhaving acetal, ketal, secondary or tertiary alkoxy alkyl, benzyloxyalkyl, substituted benzyloxy alkyl, aryloxy alkyl, dithioacetal,dithioketal, monothioacetal, monothioketal, thioether or alkoxy silanefunctional group and a very reactive functional group existing on asilica surface.

[0085] In the Equation 2, 3, or 4,

[0086] each of R and R′, which may be identical or different, ishydrogen radical, alkyl, cycloalkyl, aryl alkenyl, alkylaryl, arylalkyl,arylalkenyl radical or silane radical, and two R′ may be connected eachother to form a ring, and

[0087] R″ is alkoxy, aryloxy, alkyl, cycloalkyl, aryl, alkebyl,alkylaryl, arylakyl or arylalkenyl radical, and it may be connected withR′ to form a ring.

[0088] The reactions shown in the Equations are proved in an experimentto be practically caused on a silica surface.

[0089] Specifically, according to the Equation 5, the surface ofsilane-treated silica can block contamination by side reaction whensupporting a metallocene catalyst thereon because hydroxy groups on asilica surface are selectively removed, and the activity of a supportedcatalyst can be maximized.

[0090] As a solvent used to prepare a supported metallocene catalyst,most organic solvents including aliphatic hydrocarbon solvent such ashexane, heptane and isobutene, aromatic hydrocarbon solvent such astoluene and benzene, chlorine-substituted hydrocarbon solvent such asdichloromethane, diethylether, ether solvent such as THF, acetone,ethylacetate, etc. can be used, but an aliphatic hydrocarbon such ashexane, heptane and isobutene is preferable.

[0091] Reaction temperature is 30° C. below zero to 300° C., andpreferably room temperature to 100° C. After preparing a supportedcatalyst, a solvent is removed by layer separation and the catalyst isdried to obtain supported catalyst powder, which may be used in anolefin polymerization. Alternatively, after preparing a supportedcatalyst using the same solvent as that used in an olefin polymerizationand removing solvent by layer-separation (and, if necessary, washingseveral time with the same solvent), the catalyst slurry can be used insubsequent activation and polymerization without drying.

[0092] The prepared supported metallocene catalyst can be used in anolefin polymerization together with a cocatalyst selected from acompound represented by the Chemical Formula 6, a compound representedby the Chemical Formula 7, and a compound represented by the ChemicalFormula 8 alone or in combination.

[0093] The examples of the compounds represented by the Chemical Formula6 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane,butylaluminoxane, etc.

[0094] The examples of alkyl metal compounds represented by the ChemicalFormula 7 include trimethylaluminum, triethylaluminum,triisobutylaluminum, tripropylaluminum, tributylaluminum,dimethylchloroaluminum, dimethylisobutylaluminum, tributylaluminum,dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum,diethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum,tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum,trihexylaluminum, ethyldimethylaluminum, methyidietylaluminum,triphenylaluminum, tri-p-tollylaluminum, dimethylaluminummethoxide,dimethylaluminumethoxide, etc.

[0095] The examples of the compounds represented by the Chemical Formula8 include triethylammoniumtetraphenylborate,tributylammoniumtetraphenylborate, trimethylammoniumtetraphenylborate,tripopylammoniumtetraphenylborate,trimethylammoniumtetrakis(p-tollyl)borate,tripropylammoniumtetrakis(p-tollyl)borate,triethylammoniumtetrakis(o,p-dimethylphenyl)borate,trimethylammoniumtetrakis(o,p-dimethylphenyl)borate,tributylammoniumtetrakis(p-trifluoromethylphenyl)borate,trimethylammoniumtetrakis(p-trifluoromethylphenyl)borate,tributylammoniumtetrakispentafluorophenylborate,N,N-diethylaniliniumtetraphenylborate,N,N-diethylaniliumtetrakispentafluorophenylborate,diethylammoniumtetrakispentafluorophenylborate,triphenylphosphoniumtetraphenylborate,trimethylphosphoniumtetraphenylborate,triethylammoniumtetraphenylaluminate,tributylammoniumtetraphenyulaluminate,trimethylammoniumtetraphenylaluminate,tripropylammoniumtetraphenyulaluminate,trimethylammoniumtetrakis(p-tollyl)aluminate,tripropylammoniumtetrakis(p-tollyl)aluminate,triethylammoniumtetrakis(o,p-dimethylphenyl)aluminate,tributylammoniumtetrakis(p-trifluoromethylphenyl)aluminate,trimethylammoniumtetrakis(p-trifluoromethylphenyl)aluminate,tributylammoniumtetrakispentafluorophenylaluminate,N,N-diethylaniliumtetraphenylalumninate,N,N-diethylaniliniumtetraphenylaluminate,N,N-diethylaniliumtetrakispentafluorophenylaluminate,diethylammoniumtetrakispentafluorophenylaluminate,triphenylphosphoniumtetraphenylaluminate,trimethylphophoiumtetraphenylaluminate,triethylammoniumtetraphenylborate, tributylammoniumtetraphenylborate,trimethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate,trimethylammoniumtetrakis(p-tollyl)borate,tripropylammoniumtetrakis(p-tollyl),triethylammoniumtetrakis(o,p-dimethylphenyl)borate,trimethylammoniumtetrakis(o,p-dimethylphenyl)bporate,tributylammoniumtetrakis(p-trifluoromethylphenyl)borate,trimethylammoniumtetrakis(p-trifluoromethylphenyl)borate,tributylammoniumtetrakispentafluorophenylborate,N,N-diethylaniliniumtetraphenylborate,N,N-diethylaniliumtetraphenylborate,N,N-diethylaniliumtetrakispentafluorophenylborate,diethylammoniumtetrakispentafluorophenylborate,triphenylphosphoniumtetraphenylborate,triphenylcarboniumtetraphenylborate,triphenylcarboniumtetraphenylaluminate,triphenylcarboniumtetrakis(p-trifluoromethylphenyl)borate,triphenylcarboniumtetrakispentafluorophenylborate, etc.

[0096] As a solvent for preparing an olefin polymer using a catalystsystem consisting of the supported metallocene catalyst and thecocatalyst, C3-12 aliphatic hydrocarbon such as propane, butane,isobutene, pentane, hexane, heptane, nonane, decane and an isomerthereof, an aromatic hydrocarbon such as benzene and toluene,chloro-substituted hydrocarbon such as dichloromethane and chlorobenzenecan be used alone or in combination.

[0097] In addition, it is possible to prepare an olefin polymer usingthe metallocene compound catalyst and the cocatalyst in a gas-phase orslurry-phase without specific solvent.

[0098] Examples of olefin monomers that can be polymerized using themetallocene compound catalyst or supported metallocene catalyst and acocatalyst include ethylene, alpha-olefin, cyclic olefin, etc. and dieneolefin monomer or triene olefin monomer, polyene monomer having two ormore of double bonds can be polymerized. The examples of the monomersinclude ethylene, propylene, 2-butene, 2-pentene, 1-butene, 1-penten,4-methyl1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-icocene, norbonene,norbonadiene, ethylidenenorbonene, vinylnorbonene, dicyclopentadiene,1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene,alpha-methylstyrene, divinylbenzene, 3-chloromethylxtyrene, etc. and twoor more kinds of these monomers can be copolymerzed.

[0099] Polymerization is preferably performed at 25° C. below zero to500° C. under 0.001 to 3000 pressure, and cocatalyst is preferably addedin moles of 1 to 30000 times of metallocene moles.

[0100] In the present invention, the order of contact and introductionof a supported catalyst, a cocatalyst, a solvent and monomers are notspecifically limited. Namely, the supported metallocene catalyst andcocatalyst can be simultaneously introduced to perform a polymerization,or real polymerization can be performed after activation orprepolymerization.

[0101] The real polymerization can be performed in an appropriatesuspended solvent with introducing monomers, or it can be performed ingas-phase or slurry-phase without solvent. Prepolymer can be obtained byintroducing a supported catalyst, a cocatalyst and a solvent, agitatingat an appropriate temperature and pressure, and filtering the reactantor separating layer. Activated reactant can be obtained by the samemethod as prepolymer without olefin. In order to reducemethylaluminoxane (MAO), the supported catalyst can be firstly treatedwith an organic aluminum compound prior to using in a polymerization.

[0102] The supported metallocene catalyst of the present invention canbe effectively used in an olefinc polymerization recycling a cocatalystas described in Korean Patent Application Nos. 98-12659 and 99-3027, andin U.S. Pat. No. 6,340,728.

[0103] [Difference from the Prior Art]

[0104] U.S. Pat. No. 5,814,574 has disclosed a polymerization catalystingredient wherein a metallocene compound having Lewis acid functionalgroup selected from alkoyalkyl, heterocyclo oxygen radical or alkylheterocyclooxygen radical is supported on an inorganic carrier bybinding the metallocene compound to the inorganic carrier. In addition,U.S. Pat. No. 5,767,209 has disclosed preparation of a supportedcatalyst by binding a metallocene compound with Lewis basicity includingoxygen, silicon, phophorus, nitrogen, or sulfur to an inorganic carrierin the absence of aluminoxane, and a polymerization process bycontacting the supported catalyst with at least one olefins at atemperature and a pressure sufficient to cause a polymerization.

[0105] Examples of these Patents use butylmagnesium chloride andTiCl₄-treated silica or diethylaluminum chloride-treated silica as aninorganic carrier in order to give Leiws acidity, and usebis(tetrahydro-3-furanmethylcyclopentadienylzirconium dichloride andbis(methoxyethylcyclopentadienyl)zirconium dichloride as a catalystprecursor. And, they asserted that a metallocene compound having Lewisacid functional groups is supported on an inorganic carrier surfacethrough “binding”.

[0106] Generally, a term “binding” is used when two kinds of compoundsstill maintain each original condition even though they are boundthrough any chemical bond (‘Hackh's Chemical Dictionary’ vol. 4 writtenby Julius Grant and published from McGraw-Hill book Company explained“binding” as “holding together”). The term “binding” is used a lot forexplaining a mechanism of enzyme (‘Biochemistry’ vol. 3 pp 8-10 writtenby Lubert Stryker and published from W. H. Freeman and Company describean appropriate example.).

[0107] When the catalyst “bound” to surface through a functional groupwith Lewis basicity is activated with a cocatalyst with Lewis acidity, acatalyst is separated from surface to cause reactor fouling and particleshape becomes poor. Therefore, the catalyst is difficult to use in aslurry process or gas-phase process.

[0108] As explained, according to the present invention, a metallocenecompound having acetal, ketal, secondary or tertiary alkoxyalkyl,benzyloxy alkyl, substituted benzyloxy alkyl, aryloxy alky,dithioacetal, dithioketal, monothioacetal, monothioketal, thioether oralkoxy silane functional group on a part of its ligand is reacted with asilica dehydrated at 500° C. or more and having very reactive functionalgroups on its surface to break a carbon-oxygen bond, a carbon-sulfurbond or a silicone-oxygen bond existing on the functional group to forma novel chemical bond with a surface thereby forming a novelsilica-metallocene compound. Particularly, surface hydroxy groups areremoved by modification through silane-treatment on a silica surface andcatalyst contamination source is removed, and thus the catalyst of thepresent invention can exceed the activity of the existing catalysts evenwith a small amount.

[0109] Comparative Examples 3 and 4 show that the supported catalyst ofthe present invention differs from those of U.S. Pat. Nos. 5,814,574 and5,767,209. Specifically, when [2-ethoxyethyl-O—(CH₂)₆—C₅H₄]ZrCl₂, whichhas similar structure to the catalysts used in the Examples of thePatents, has relatively high Lewis basicity because it consists ofprimary alkyl only, and has a structure good to binding because it has 4oxygen atoms, is used in a polymerization while using the silica used inthe present invention having very reactive siloxane group or MgCl₂described as a preferable carrier in line 4, column 57 of the U.S. Pat.No. 5,814,574 as a carrier, fouling seriously occurred and particleshape could not be controlled.

[0110] Meanwhile, [t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ compound that hast-butyl ether group with little Lewis basicity due to a steric hindranceeffectively causes support reaction asserted in the present invention,and thus no fouling occurs and particle shape can be controlled. It isknown that t-butylether can be effectively used as a protection groupfor alcohol because it has little Lewis basicity and t-butyl group canbe broken relatively easily (Tetraherdron Letter, vol 29, 1988, 2951 p).

[0111] Specifically, when the supported catalyst bound to surfacethrough Lewis base functional groups claimed in the above patents isactivated with aluminoxane during polymerization reaction, aluminoxaneis separated from surface because it has Lewis acidity, and thus reactorfouling occurs and produced particle shape is not uniform, rendering itunusable in a slurry or gas-phase polymerization. It is well known thataluminoxane has Lewis acidity (J. Am. Chem. Soc. 1995, vol. 117, p6465).

[0112] In addition, when a catalyst having no functional group capableof reacting with silica as claimed in U.S. Pat. No. 5,324,800, whichmaybe bound to a carrier surface through week bonds, is activated withaluminoxane, aluminoxane is separated from surface, and thus reactorfouling occurs and produced particle shape is not uniform, rendering itunusable in a slurry or gas-phase polymerization (Comparative Example3).

[0113] When the supported metallocene catalyst of the present invention,wherein a part of a ligand of metallocene compound is attached to asilica surface through strong chemical bond by reacting acetal, ketal,secondary or tertiaty alkoxy alkyl, benzyloxy alkyl, substitutedbenzyloxy alkyl, aryloxy alkyl, dithioacetal, dithioketal,monothioacetal, monothioketal, thioether or alkoxysilane functionalgroup with a silica dehydrated at high temperature of 500° C. or moreand having highly reactive functional group on its surface to breakcarbon-oxygen, carbon-sulfur or silicon-oxygen bond existing on thefunctional group thereby forming a novel chemical bond with a surface,is activated with a cocatalyst such as aluminoxane, nothing is separatedfrom the surface and thus reactor fouling does not occur when polyolefinis prepared by slurry or gas-phase polymerization, and particle shapeand apparent density of produced polymer is superior, rendering itsuitable for slurry or gas-phase polymerization process.

[0114] The present invention will now be explained in more detail withreference to the following Examples and Comparative Examples. However,these are to illustrate the present invention and the present inventionis not limited to them.

EXAMPLE

[0115] Organic reagent and solvent required in catalyst preparation andpolymerization are Aldirch Company products and they are purified bystandard method. Ethylene is polymerized after passing through moistureand oxygen filtering equipment a high-purity product from Applied GasTechnology Company, and contact with air and moisture is blocked in allsteps of catalyst synthesis, support and polymerization to enhance thereproductiveness of the experiment.

[0116] In order to prove structure of a catalyst, spectrum was obtainedusing 300 MHz NMR (Brucker).

[0117] An apparent density was measured according to the methods set inDIN 53466 and ISO R 60 using an apparent density tester (APT Institutefr Prftechnik product. Apparent Density Tester 1132).

Example 1

[0118] (Synthesis of [t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂)

[0119] t-Butyl-O—(CH₂)₆—Cl was prepared from 6-chlorohexanol accordingto the process described in Tetrahedron Lett. 2951, 1988. 1 equivalentof NaCp (2.0 M THF solution) was introduced therein and the reactant wasagitated overnight at room temperature. Water was added thereto toseparate an organic layer, the organic layer was dehumidified with MgSO₄anhydride and solvent was removed therefrom, and then it wasvacuum-distilled to obtain t-butyl-O—(CH₂)₆—C₅H₅ (80° C./0.1 mmHg).Yield from 6-chlorohexanol was 56%.

[0120] 1.349 g of the compound were dissolved in 5 Ml of THF and 1equivalent of hexane solution was introduced therein at 40° C.Temperature of the solution was slowly elevated to room temperature andthe solution was agitated for 3 hours. The solution was introduced in aflask including 0.5 equivalents of ZrCl₄(THF)₂ and agitated at 55° C.for 40 hours. Solvent was removed by distillation, and 30 Ml of hexanewere added thereto and hexane was removed by filtering while hot toobtain 1.711 g of desired product (yield 92%). The compound was used toprepare a supported catalyst without further purification (yield 60%,b.p. approximately 80° C./approximately 0.11 mmHg).

[0121]¹H NMR (300 MHz, CDCl3): 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7 1.3 (m, 8H), 1.17(s, 9H).

[0122]¹³C NMR (CDCl3): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66,30.61, 30.14, 29.18, 27.58, 26.00.

[0123] (Preparation of Surface-Modified Carrier)

[0124] Silica (Grace Davison Company product XPO 2412) was dehydrated at800° C. for 5 hours while adding vacuum. 10.0 g of dehydrated silicawere introduced in a glass reactor and a dropping funnel was equipped. Adropping funnel was closed and silica was vacuum-dried for approximately2 hours.

[0125] 25 Ml of hexane where 3 mmol of hexamethyl disilazane weredissolved were incorporated in the dropping funnel, and then they wereadded to silica of vacuum condition under nitrogen pressurization. 30 Mlof hexane were further added, and the reactant was reacted whileagitating at 70° C. for 2 hours. Hexane was removed by layer-separation,and then the reactant was washed with 30 Ml of hexane 3 to 5 times whileobserving color change with litmus test paper. After washing, remaininghexane solution was removed using a cannular, and then hexane wascompletely removed by pressurizing while slowly elevating temperature to300° C. The reactant was vacuum-dried under 0.1 mmHg for 4 hours whilemaintaining temperature of 300° C. to obtain siliazane-treated silicacarrier.

[0126] (Preparation of a Supported Catalyst)

[0127] 1.0 g of the silazane-treated silica (Grace Davison Companyproduct XPO 2412) were introduced in a glass reactor, 40 Ml of hexanewere added thereto, and 10 Ml hexane where 200 mg of[t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ catalyst were dissolved were addedthereto. The mixture was reacted while agitating at 85° C. for 3 hours.Hexane was removed by layer-separation, washing with 30 ml of hexane anddepressurization to obtain a supported catalyst.

[0128] (Polymerization)

[0129] 100 mg of the prepared supported catalyst were quantified andincorporated into a glass reactor in a dry box, and then the reactor wasclosed and taken out of the dry box. Then, 50 ml of purified hexane wereintroduced in the reactor and aluminoxane (MAO) where heptane or hexanewas dissolved were introduced therein in an amount corresponding to 1.0mmol-Al. The mixture was agitated at 40° C. for 30 minutes, 30 psig ofethylene pressure was added thereto and the mixture was further agitatedat room temperature for 30 minutes to perform prepolymerization.

[0130] To an 1 liter-Buchi reactor including 660 ml of hexane where1.50mmol of triethylaluminum are dissolved, the prepared prepolymerizationcatalyst was introduced without contact with air, and thenpolymerization was performed at 80° C. while continuously addingpressure of 130 psig. Ethylene was evaporated and the reactant wasfiltered while opening the reactor, and then the reactant was dehydratedin an oven of 80° C. to obtain a polymer.

[0131] The amount (activity) of produced polyethylene for the preparedcatalyst was 115 g. The apparent density of obtained polymer wasmeasured to approximately 0.35 g/ml and no reactor fouling occurred.

Comparative Example 1

[0132] A supported catalyst was prepared by the same method as inExample 1, using t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ prepared in Example 1 as acatalyst and silica (Grace Davison Company product XPO 2412) which wasdehydrated with adding vacuum at 800° C. for 5 hours withoutsilazane-treatment as a carrier, and then prepolymerization and realpolymerization were performed. The amount (activity) of producedpolyethylene was 90 g, no fouling occurred during prepolymerization andreal polymerization, produced particle shape was good, and apparentdensity was 0.34 g/ml.

Comparative Example 2

[0133] A supported catalyst was prepared by the same method as inExample 1, using bis(octylcyclopentadienyl)zirconium dichloride havingno functional group capable of reacting with silica as claimed in U.S.Pat. No. 5,324,800 as a catalyst and the silazane-treated silicaprepared in Example 1 as a carrier, and then prepolymerization andpolymerization were peroformed. The amount (activity) of producedpolyethylene was 51 g, fouling seriously occurred duringprepolymerization and poymerization, produced particle shape was notgood, and apparent density was 0.05 g/ml.

Comparative Example 3

[0134] A compound [2-ethoxyethyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂, which has asimilar structure to those used in Examples of U.S. Pat. Nos. 5,814,574and 5,767,209, has relatively high Lewis basicity because it consists ofprimary alkyl only, and has a good structure to binding because it has 4oxygen atoms, was synthesized by the method described in J. Organomet.Chem. Vol. 552 (1998), 313), and it was supported on a dried silica thatis not silane-treated by the same method as in Example 1, and thenprepolymerization and real polymerization were performed.

[0135] The amount of produced polyethylene was very small as 10.7 g,fouling seriously occurred, and particle shape could not be controlledand thus an apparent density was 0.06 g/ml.

Comparative Example 4

[0136] A supported catalyst wherein [2-ethoxyethyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂used in Example 3 is supported on a MgCl₂ carrier described as apreferable carrier in line 4, column 57 of U.S. Pat. No. 5,814,574through “binding” was used for polymerization.

[0137] 26.5 mg of [2-ethoxyethyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ were mixed with500 mg of MgCl₂ anhydride pulverized with a ball mill, the mixture wasagitated at room temperature for 2 hours in the presence of 30 ml ofhexane. Hexane was removed by layer-separation, and the mixture waswashed again with 50 ml of hexane and vacuum depressurized to removeremaining hexane. 100 mg of the supported catalyst was introduced in aglass reactor, 250 ml of hexane was added thereto, 1.6 ml of MAO wereintroduced therein, and then the mixture was agitated at 80° C. for 5minutes in an incubator. Polymerization was performed with adding 40psig of ethylene.

[0138] Reactor fouling occurred, and particle shape could not becontrolled well. The amount of produced polyethylene (PE) was 7.4 g, andan apparent density was 0.10 g/ml. TABLE 1 Catalyst Carrier ActivityExample 1 [t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ HMDS-SiO₂ 115 ComparativeExample 1 [t-butyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ SiO₂ 90 Comparative Example 2[CH₃(CH₂)₇—C₅H₄]₂ZrCl₂ HMDS-SiO2 51 Comparative Example 3[2-ethoxyethyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ SiO2 10.7 Comparative Example 4[2-ethoxyethyl-O—(CH₂)₆—C₅H₄]₂ZrCl₂ MgCl2 7.4

[0139] Since in the supported metallocene catalyst of the presentinvention, a part of a ligand of a metallocene compound is attached to asilica surface through strong chemical bonds, no catalyst is separatedfrom the surface when activated, and thus no reactor fouling occurs whenpreparing polyolefin by slurry or gas-phase polymerization, and particleshape and apparent density of produced polymer are superior, renderingit suitable for a slurry of gas-phase polymerization process.

What is claimed is:
 1. A supported metallocene catalyst wherein ametallocene compound is supported on a carrier by contact reacting a)one or more kinds of metallocene compound catalyst ingredient wherein atleast one hydrogen radical existing on R1, R2 or B of metallocenecompound represented by the following Chemical Formula 1 or 2 issubstituted with an organic radical selected from a group consisting ofa radical represented by the following Chemical Formula 3, a radicalrepresented by the following Chemical Formula 4 and a radicalrepresented by the following Chemical Formula 5; and b) a carrier, inthe presence of an organic solvent to break a carbon-oxygen bond, acarbon-sulfur bond or a silicon-oxygen bond existing on a radicalrepresented by the following Chemical Formula 3, 4 or 5 of the a)metallocene compound catalyst ingredient thereby forming a novelchemical bond between the a) metallocene compound and the b) carrier,characterized in that the b) carrier is a silica prepared bysilane-treating a silica dehydrated at 500° C. or more to selectivelyremove hydroxy groups out of hydroxy groups and siloxane groups existingon a silica surface: (C₅R¹ _(m))_(p)B_(s)(C₅R¹ _(m))MQ_(3-p)  [ChemicalFormula 1]

[Chemical Formula 2] M is Group 4 transition metal, (C₅R¹ _(m)) and(C₅R¹ _(n)) are independently a cyclopentadienyl or substitutedcyclopentadienyl ligand wherein each R¹, which may be identical ordifferent, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl, arylalkenyl radical or hydrocarbyl-substitutedGroup 14 metalloid, or a substituted cyclopentadienyl ligand wherein twoneighboring carbon atoms in C₅ are connected each other through ahydrocarbyl radical to form one or more 4-16 angular rings; B, which isa bridge connecting two cyclopentadienyl ligands or one cyclopentadienylligand and JR² _(z-y) through covalent bonds, is carbon chain alkylene,carbon chain arylene, carbon chain alkenylene, dialkylsilicone,dialkylgermanium, alkyl phosphine or alkylamine; R² is hydrogen radical,C1-40 alkyl radical, alkenyl radical, aryl radical, alkylaryl radical,or arylalkyl radical; J is a VA Group atom or a VIA Group atom; Q, whichmay be identical or different, is halogen radical, C1-20 alkyl radical,alkenyl radical, aryl radical, alkylaryl radical, arylakyl radical orC1-20 alkylidene radical; L is a Lewis base; s is 0 or 1, and p is 0, 1or 2, provided that s is 0 when p is 0, m is 4 when s is 1, m is 5 whens is 0; z is an atomic valence of J, which is 3 for VA Group atoms and 2for VIA Group atoms; and x is 0 or 1, provided that when x is 0, n is 5,y is 1, and w is more than 0, and when x is 1, n is 4, y is 2, and w is0.)

[Chemical Formula 3] Z is an oxygen or sulfur atom; R, which may beidentical or different, is hydrogen radical, C1-40 alkyl, cycloalkyl,aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; R′, whichmay be identical or different, is hydrogen radical, C1-40 alkyl,cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylakneyl radical,and two R′ may be connected with each other to form a ring; Y is C1-40alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, andit may be connected with R′ to form a ring; provided that when Z is asulfur atom, Y must be alkoxy or aryloxy, and when Y is alkylthio,arylthio, phenyl or substituted phenyl, Z must be an oxygen atom; and Ais a carbon or silicon atom.)

[Chemical Formula 4] Z is an oxygen or sulfur atom, and at least one Zis an oxygen atom; R″ is hydrogen radical, C1-40 alkyl, cycloalkyl,arylalkenyl, alkylaryl, arylalkyl, or arylalkenyl radical, and it may beconnected with R′″ to form a ring; R′″, which may be identical ordifferent, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl, or arylalkenyl radical, and two R′″ may beconnected with each other to form a ring; and A is a carbon or siliconatom.)

[Chemical Formula 5] R″″, which may be identical or different, ishydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl,arylalkyl, or arylalkenyl radical; R′″″, which may be identical ordifferent, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl, or arylalkenyl radical, and two neighboring R′″″may be connected with each other to form a ring; provided that when atleast one R″″ is hydrogen radical, all R′″″ is not a hydrogen radical,and when at least one R′″″ is hydrogen radical, all R″″ is not hydrogenradical; and A is carbon or silicon atom.)
 2. The supported metallocenecatalyst according to claim 1, wherein the silane is an organosilanerepresented by the following Chemical Formula 9 or 10:(R⁵Si)₂NH  [Chemical Formula 9]R_(l)SiX_(4-l)  [Chemical Formula 10] (Inthe Chemical Formula 9 or 10, R is hydrogen radical or hydrocarbylfunctional group; X is halogen atom; and l is 1, 2 or 3.)
 3. A processfor polymerizing an olefin using a catalyst system comprising a) asupported metallocene catalyst wherein a metallocene compound issupported on a carrier by contact reacting i) one or more kinds ofmetallocene catalyst compound ingredient wherein at least one hydrogenradical existing on R1, R2 or B of metallocene compound represented bythe following Chemical Formula 1 or 2 is substituted with a radicalselected from a group consisting of a radical represented by thefollowing Chemical Formula 3, a radical represented by the followingChemical Formula 4 and a radical represented by the following ChemicalFormula 5; and ii) a carrier, in the presence of an organic solvent tobreak a carbon-oxygen bond, carbon-sulfur bond or silicon-oxygen bondexisting on a radical represented by the following Chemical Formula 3, 4or 5 of the i) metallocene catalyst ingredient thereby forming a novelchemical bond between the i) metallocene catalyst and ii) a carrier; andb) a cocatalyst seleceted from a group consisting of a compoundrepresented by the following Chemical Formula 6, a compound representedby the following Chemical Formula 7 and a compound represented by thefollowing Chemical Formula 8, characterized in that the a) ii) carrieris a silica prepared by silane-treating a silica dehydrated at 500° C.or more to selectively remove hydroxy groups out of hydroxy groups andsiloxane groups existing on a silica surface: (C₅R¹ _(m))_(p)B_(s)(C₅R¹_(m))MQ_(3-p)  [Chemical Formula 1]

M is Group 4 transition metal, (C₅R¹ _(m)) and (C₅R¹ _(n)) areindependently a cyclopentadienyl or substituted cyclopentadienyl ligandwherein each R1, which may be identical or different, is hydrogenradical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl,arylalkenyl radical or hydrocarbyl-substituted Group 14 metalloid, or asubstituted cyclopentadienyl ligand wherein two neighboring carbon atomsin C5 are connected each other through a hydrocarbyl radical to form oneor more 4-16 angular rings; B, which is a bridge connecting twocyclopentadienyl ligand or one cyclopentadienyl ligand and JR² _(z-y)through covalent bonds, is carbon chain alkylene, carbon chain arylene,carbon chain alkenylene, dialkylsilicone, dialkylgermanium, alkylphosphine or alkylamine; R² is hydrogen radical, C1-40 alkyl radical,alkenyl radical, aryl radical, alkylaryl radical, or arylalkyl radical;J is a VA Group atom or VIA Group atom; Q, which may be identical ordifferent, is halogen radical, C1-20 alkyl radical, alkenyl radical,aryl radical, alkylaryl radical, arylakyl radical or C1-20 alkylideneradical; L is a Lewis base; s is 0 or 1, and p is 0, 1 or 2, providedthat s is 0 when p is 0, m is 4 when s is 1, m is 5 when s is 0; z is anatomic valence of J, which is 3 for VA Group atoms and 2 for VIA Groupatoms; and x is 0 or 1, provided that when x is 0, n is 5, y is 1, and wis more than 0, and when x is 1, n is 4, y is 2, and w is 0.)

Z is an oxygen or sulfur atom; R, which may be identical or different,is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl,arylalkyl, or arylalkenyl radical; R′, which may be identical ordifferent, is hydrogen radical, C1-40 alkyl, cycloalkyl, aryl, alkenyl,alkylaryl, arylalkyl, or arylakneyl radical, and two R′ may be connectedwith each other to form a ring; Y is C1-40 alkoxy, aryloxy, alkylthio,arylthio, phenyl or substituted phenyl, and it may be connected with R′to form a ring; provided that when Z is a sulfur atom, Y must be alkoxyor aryloxy, and when Y is alkylthio, arylthio, phenyl or substitutedphenyl, Z must be an oxygen atom; and A is a carbon or silicon atom.)

Z is an oxygen or sulfur atom, and at least one is an oxygen atom; R″ ishydrogen radical, C1-40 alkyl, cycloalkyl, arylalkenyl, alkylaryl,arylalkyl, or arylalkenyl radical, and it may be connected with R′″ toform a ring; R′″, which may be identical or different, is hydrogenradical, C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl,or arylalkenyl radical, and two R′″ may be connected with each other toform a ring; and A is a carbon or silicon atom.)

R″″, which may be identical or different, is hydrogen radical, C1-40alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenylradical; R′″″, which may be identical or different, is hydrogen radical,C1-40 alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, orarylalkenyl radical, and two neighboring R′″″ may be connected with eachother to form a ring; provided that when at least one R″″ is hydrogenradical, all R′″″ is not a hydrogen radical, and when at least one R′″″is hydrogen radical, all R″″ is not hydrogen radical; and A is carbon orsilicon atom.)

R³, which may be identical or different, is halogen radical, C1-40hydrocarbyl radical or halogen substituted C1-40 hydrocarbyl radical;and d is an integer of 2 or more.) Al(R⁴)₃  [Chemical Formula 7] (In theChemical Formula 7, R⁴, which may be identical or different, is halogenradical, C1-40 hydrocarbyl radical or halogen substituted C1-40hydrocarbyl radical) [L]⁺[NE₄]⁻  [Chemical Formula 8] (In the ChemicalFormula 8, [L]⁺ is a cation consisting of inorganic organic group; N isa Group 13 atom on periodic table; and E, which may be identical ordifferent, is C6-40 arylradical substituted with one or more of halogenradical, C1-40 hydrocarbyl, alkoxy, phenyl radical, or C1-40 hydrocarbylradical comprising nitrogen, phosphorus, sulfur and oxygen atoms)
 4. Theprocess for polymerizing an olefin according to claim 3, wherein thesilane is an organosilane represented by the following Chemical Formula9 or 10: (R₃Si)₂NH  [Chemical Formula 9]R^(l)SiX_(4-l)  [ChemicalFormula 10] (In the Chemical Formula 9 or 10, R is hydrogen radical orhydrocarbyl functional group; X is halogen atom; and l is 1, 2 or 3.) 5.The process for polymerizing an olefin according to claim 3, wherein theb) cocatalyst is one or more kinds of compounds selected from a compoundrepresented by the above Chemical Formula 6 and a compound representedby the above Chemical Formula
 7. 6. The process for polymerizing anolefin according to claim 3, wherein the a) i) metallocene compound is[Z-O—(CH₂)_(a)—C₅H₄]₂ZrCl₂ (wherein a is 4˜8, Z is selected from a groupconsisting of methoxymethyl, t-butoxymethyl, tetrahydropyranyl,tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1methopxyethyl and t-butyl)and the b) cocatalyst is one or more kinds of compounds selected from agroup consisting of a compound represented by the above Chemical Formula6 and a compound represented by the above Chemical Formula
 7. 7. Theprocess for polymerizing an olefin according to claim 3, wherein thepolymerization is a slurry polymerization or a gas-phase polymerization.